Method for producing asymmetrical 4,6-bis(aryloxy)pyrimidine derivatives

ABSTRACT

The invention relates to a novel process for preparing known asymmetrical 4,6-bis(aryloxy)pyrimidine derivatives.

[0001] The invention relates to a novel process for preparing knownasymmetric 4,6-bis(aryloxy)pyrimidine derivatives.

[0002] Asymmetric 4,6-bis(aryloxy)pyrimidine derivatives are known andare used, for example, as pesticides in crop protection (cf. WO94/02470, WO 97/27189, WO 98/21189, WO 99/57116).

[0003] The preparation of asymmetric 4,6-bis(aryloxy)pyrimidinederivatives is more difficult than the preparation of symmetric4,6-bis(aryloxy)pyrimidine compounds since the different aryloxy groupshave to be introduced in separate reactions.

[0004] A plurality of processes for preparing asymmetric4,6-bis(aryloxy)pyrimidine derivatives has already been disclosed.

[0005] WO 94/02470 describes the preparation of asymmetric4,6-bis(aryloxy)pyrimidine derivatives by a two-step process. Reactionof 4,6-dichloropyrimidine (A) with one equivalent of a phenol derivative(B) under basic reaction conditions and subsequent reaction with asecond phenol derivative (D) gives asymmetric 4,6-bis(aryloxy)pyrimidinederivatives (E) (cf. Scheme 1).

[0006] This process has the disadvantage that an exchange of the aryloxygroups takes place in the second reaction step, giving a product mixtureof asymmetric 4,6-bis(aryloxy)pyrimidine derivatives (E) and thesymmetric 4,6-bis(aryloxy)pyrimidine derivatives (F) and (G).

[0007] As a consequence, the asymmetric 4,6-bis(aryloxy)pyrimidinederivatives (E) are obtained in poor yield and can only be isolated bycomplicated separation methods.

[0008] To avoid the problem of the exchange of the aryloxy groups to thesecond reaction step, it is possible to use the starting material4,6-difluoropyrimidine (cf. Scheme 2 and WO 94/02470, EP-A1-794 177).

[0009] However, this process has the disadvantage that4,6-difluoropyrimidine has to be prepared by a chlorine/fluorineexchange, starting from 4,6-dichloro-pyrimidine. The preparation ofasymmetric 4,6-bis(aryloxy)pyrimidine derivatives therefore requires anadditional reaction step. Preferred starting materials are therefore4,6-dichloropyrimidine or 4,6-dichloropyrimidine derivatives.

[0010] The preparation of asymmetric 4,6-bis(aryloxy)pyrimidinederivatives starting from 4,6-dichloro-5-halogeno-pyrimidineanalogously, to the process described in WO 94/02470 is described in WO98/41513.

[0011] EP-A1-794 177, U.S. Pat. No. 5,849,910 and U.S. Pat. No.5,977,363 describe a further process for preparing asymmetric4,6-bis(aryloxy)pyrimidine derivatives (E) starting from4,6-dichloropyrimidine (A) (cf. Scheme 3).

[0012] In this process, the aryloxy-chloropyrimidine derivative (C)obtained after the first reaction step is treated with at least onemolar equivalent of a tertiary amine.

[0013] The intermediates formed are pyrimidinyl-ammonium derivatives(J), which are reacted with phenol derivatives (D) to give asymmetrical4,6-bis(aryloxy)pyrimidine derivatives (E).

[0014] This process has the disadvantage that at least equivalent molaramounts of the tertiary amine are required, which can only be recoveredusing complicated procedures. Moreover, the asymmetric4,6-bis(aryloxy)pyrimidine derivatives are only obtained in moderateyields. This process is therefore unsuitable for the large-scaleindustrial preparation, especially if expensive amines are used.

[0015] It has now been found that asymmetric 4,6-bis(aryloxy)pyrimidinederivatives of the general formula (I),

[0016] in which

[0017] Ar¹ represents in each case substituted or unsubstituted aryl orheterocyclyl,

[0018] X represents hydrogen, fluorine, chlorine or bromine,

[0019] L¹, L², L³, L⁴ and L⁵ are identical or different andindependently of one another each represents hydrogen, halogen, cyano,nitro, alkylcarbonyl formyl, alkoxycarbonyl, aminocarbonyl,alkylaminocarbonyl, dialkylaminocarbonyl, in each case optionallyhalogen-substituted alkyl, alkoxy, alkylthio, alkylsulphinyl oralkylsulphonyl, or

[0020] L¹, L², L³ and L⁴ are identical or different and independently ofone another each represents hydrogen, halogen, cyano, nitro,alkylcarbonyl, formyl, alkoxycarbonyl, aminocarbonyl,alkylaminocarbonyl, dialkylaminocarbonyl, in each case optionallyhalogen-substituted alkyl, alkoxy, alkylthio, alkylsulphinyl oralkylsulphonyl, and

[0021] L⁵ represents one of the groups below:

[0022] where * denotes the point of attachment to the phenyl radical,and where the radicals

[0023] are different, are obtained when 4,6-dichloropyrimidinederivatives of the general formula (II),

[0024] in which

[0025] X is as defined above,

[0026] a) are initially, in a first step, reacted with compounds of thegeneral formula (III),

Ar¹—OH,  (III)

[0027]  in which

[0028] Ar¹ is as defined above,

[0029] if appropriate in the presence of a diluent and if appropriate inthe presence of an acid acceptor,

[0030] and the resulting compounds of formula (IV),

[0031]  in which

[0032] Ar¹ and X are each as defined above

[0033] are then, in a second step, reacted with compounds of the generalformula (V),

[0034] L¹, L², L³, L⁴ and L⁵ are each as defined above,

[0035] if appropriate in the presence of a solvent, if appropriate inthe presence of a base and with addition of from 2 to 40 mol % of1,4-diazabicyclo[2.2.2]octane (DABCO), or

[0036] b) are initially, in a first step, reacted with compounds of thegeneral formula (V),

[0037]  in which

[0038] L¹, L², L³, L⁴ and L⁵ are each as defined above,

[0039] if appropriate in the presence of a diluent and if appropriate inthe presence of an acid acceptor,

[0040] and the resulting compounds of the formula (VI),

[0041]  in which

[0042] X, L¹, L², L³, L⁴ and L⁵ are each as defined above,

[0043] are then, in a second step, reacted with compounds of generalformula (III),

Ar¹—OH,  (III)

[0044]  in which

[0045] Ar¹ is as defined above,

[0046] if appropriate in the presence of a solvent, if appropriate inthe presence of a base and with addition of from 2 to 40 mol % of1,4-diazabicyclo[2.2.2]octane (DABCO).

[0047] In the definitions, the saturated or unsaturated hydrocarbonchains, such as alkyl, alkanediyl, alkenyl or alkinyl, are in each casestraight-chain or branched, including in combination with heteroatoms,such as, for example, in alkoxy, alkylthio or alkylamino. Unlessindicated otherwise, preference is given to hydrocarbon chains having 1to 6 carbon atoms. Unless indicated otherwise, hydrocarbon chains having2 to 6 carbon atoms are preferred for alkenyl or alkinyl.

[0048] Halogen generally represents fluorine, chlorine, bromine oriodine, preferably fluorine, chlorine or bromine, in particular fluorineor chlorine.

[0049] Aryl represents aromatic, mono- or polycyclic hydrocarbon rings,such as, for example, phenyl, naphthyl, anthranyl, phenanthryl,preferably phenyl or naphthyl, in particular phenyl.

[0050] Heterocyclyl represents saturated or unsaturated, and alsoaromatic, cyclic compounds where at least one ring member is aheteroatom, i.e. an atom different from carbon. If the ring contains aplurality of heteroatoms, this can be identical or different. Preferredheteroatoms are oxygen, nitrogen or sulphur. If the ring contains aplurality of oxygen atoms, these are adjacent. If appropriate, thecyclic compounds form a polycyclic ring system together with othercarbocyclic or heterocyclic, fused-on or bridged rings. Preference isgiven to mono- or bicyclic ring systems, in particular to mono- orbicyclic aromatic ring systems.

[0051] Cycloalkyl represents saturated carbocyclic compounds which, ifappropriate, form a polycyclic ring system together with othercarbocyclic fused-on or bridged rings.

[0052] A polycyclic ring system can be attached to a heterocyclic ringor a fused-on carbocyclic ring. This heterocyclyl group can also bemono- or polysubstituted, preferably by methyl, ethyl or halogen.Preference is given to mono- or bicyclic ring systems, in particularmono- or bicyclic aromatic ring systems.

[0053] Halogenoalkoxy represents partially or fully halogenated alkoxy.In the case of polyhalogenated halogenoalkoxy, the halogen atoms can beidentical or different. Preferred halogen atoms are fluorine andchlorine, in particular fluorine. If the halogenoalkoxy additionallycarries other substituents, the maximum number of halogen atoms possibleis reduced to the remaining free valencies. Unless indicated otherwise,preference is given to hydrocarbon chains having 1 to 6 carbon atoms.

[0054] Halogenoalkyl represents partially or fully halogenated alkyl. Inthe case of polyhalogenated halogenoalkyl, the halogen atoms can beidentical or different. Preferred halogen atoms are fluorine andchlorine, in particular fluorine. If the halogenoalkyl additionallycarries other substituents, the maximum number of halogen atoms possibleis reduced to the remaining free valencies. Unless indicated otherwise,preference is given to hydrocarbon chains having 1 to 6 carbon atoms.

[0055] The starting materials of the formulae (III) and (V), theintermediates of the formulae (IV) and (VI) and the end products of thegeneral formula (I) can be present as pure isomers of different possibleisomeric forms, for example E or Z isomers or, as appropriate, asmixtures of different possible isomeric forms, in particular ofheteroisomers, such as for example, E/Z mixtures.

[0056] In general, Ar¹ represents, in particular:

[0057] heterocyclyl having 3 to 7 ring members which is optionallysubstituted by halogen or by alkyl, alkoxy, halogenoalkyl,halogenoalkoxy having in each case 1 to 4 carbon atoms;

[0058] or represents phenyl or naphthyl, each of which is optionallymono- to tetrasubstituted by identical or different substituents, thepossible substituents preferably being selected from the list below:

[0059] halogen, cyano, nitro, formyl, carboxyl, carbamoyl,thiocarbamoyl;

[0060] in each case straight-chain or branched alkyl, oxoalkyl, alkoxy,alkoxyalkyl, alkylthioalkyl, dialkoxyalkyl, alkylthio, alkylsulphinyl oralkylsulphonyl having in each case 1 to 8 carbon atoms;

[0061] in each case straight-chain or branched alkenyl or alkenyloxyhaving in each case 2 to 6 carbon atoms;

[0062] in each case straight-chain or branched halogenoalkyl,halogenoalkoxy, halogenoalkylthio, halogenoalkylsulphinyl orhalogenoalkylsulphonyl having in each case 1 to 6 carbon atoms and 1 to13 identical or different halogen atoms;

[0063] in each case straight-chain or branched halogenoalkenyl orhalogenoalkenyloxy having in each case 2 to 6 carbon atoms and 1 to 11identical or different halogen atoms;

[0064] in each case straight-chain or branched dialkylamino;

[0065] alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl,alkylaminocarbonyl, dialkylaminocarbonyl, arylalkylaminocarbonyl,dialkylaminocarbonyloxy, alkenylcarbonyl or alkinylcarbonyl, having 1 to6 carbon atoms in the respective hydrocarbon chain;

[0066] cycloalkyl or cycloalkyloxy having in each case from 3 to 6carbon atoms;

[0067] in each case doubly attached alkylene having 3 or 4 carbon atoms,oxyalkylene having 2 or 3 carbon atoms or dioxyalkylene having 1 or 2carbon atoms, each of which is optionally mono- to tetrasubstituted byidentical or different substituents from the group consisting offluorine, chlorine, oxo, methyl, trifluoromethyl and ethyl;

[0068]  or a grouping

[0069] in which

[0070] A¹ represents hydrogen, hydroxyl or alkyl having 1 to 4 carbonatoms or cycloalkyl having 1 to 6 carbon atoms and

[0071] A² represents hydroxyl, methoxy, ethoxy, amino, methylamino,phenyl, benzyl or represents in each case optionally cyano-, alkoxy-,alkylthio-, alkylamino-, dialkylamino- or phenyl-substituted alkyl oralkoxy having 1 to 4 carbon atoms, or represents alkenyloxy oralkinyloxy having in each case 2 to 4 carbon atoms,

[0072] and also phenyl, benzoyl, benzoylethenyl, cinnamoyl, heterocyclylor phenylalkyl, phenylalkyloxy or heterocyclylalkyl, having in each case1 to 3 carbon atoms in the respective alkyl moieties and being in eachcase optionally mono- to trisubstituted in the ring moiety by halogenand/or straight-chain or branched alkyl or alkoxy having 1 to 4 carbonatoms.

[0073] Preference is given to compounds in which Ar¹ represents:

[0074] optionally methyl-, ethyl-, methoxy-, ethoxy-, trifluoromethyl-or trifluoromethoxy-substituted thienyl, pyridyl or furyl;

[0075] or represents phenyl which is in each case optionally mono- totetrasubstituted by identical or different substituents, the possiblesubstituents preferably being selected from the list below:

[0076] fluorine, chlorine, bromine, iodine, cyano, nitro, formyl,carboxyl, carbamoyl, thiocarbamoyl,

[0077] methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, 1-, 2-, 3-,neo-pentyl, 1-, 2-, 3-, 4-(2-methylbutyl), 1-, 2-, 3-hexyl, 1-, 2-, 3-,4-, 5-(2-methylpentyl), 1-, 2-, 3-(3-methylpentyl), 2-ethylbutyl, 1-,3-, 4-(2,2-dimetylbutyl), 1-, 2-(2,3-dimethylbutyl), 3-oxobutyl,methoxymethyl, dimethoxymethyl,

[0078] methoxy, ethoxy, n- or i-propoxy,

[0079] methylthio, ethylthio, n- oder i-propylthio, methylsulphinyl,ethylsulphinyl, methylsulphonyl or ethylsulphonyl,

[0080] vinyl, allyl, 2-methylallyl, propene-1-yl, crotonyl, propargyl,vinyloxy, allyloxy, 2-methylallyloxy, propene-1-yloxy, crotonyloxy,propargyloxy,

[0081] trifluoromethyl, trifluoroethyl,

[0082] difluoromethoxy, trifluoromethoxy, difluorochloromethoxy,trifluoroethoxy, difluoromethylthio, trifluoromethylthio,difluorochloromethylthio, trifluoromethylsulphinyl ortrifluoromethylsulphonyl,

[0083] dimethylamino, diethylamino,

[0084] acetyl, propionyl, methoxycarbonyl, ethoxycarbonyl,methylaminocarbonyl, ethylaminocarbonyl, dimethylaminocarbonyl,diethylaminocarbonyl, dimethylaminocarbonyloxy, diethylaminocarbonyloxy,benzylaminocarbonyl, acryloyl, propioloyl,

[0085] cyclopentyl, cyclohexyl,

[0086] in each case doubly attached propanediyl, ethyleneoxy, each ofwhich is optionally mono- to tetrasubstituted by identical or differentsubstituents from the group consisting of fluorine, chlorine, oxo,methyl and trifluoromethyl,

[0087]  or a grouping

[0088] where

[0089] A¹ represents hydrogen, methyl of hydroxyl and

[0090] A² represents hydroxyl, methoxy, ethoxy, amino, methylamino,phenyl or benzyl, and also

[0091] phenyl, benzoyl, benzoylethenyl, cinnamoyl, benzyl, phenylethyl,phenylpropyl, benzyloxy, 5,6-dihydro-1,4,2-dioxazin-3-ylmethyl,triazolylmethyl, benzoxazol-2-ylmethyl, 1,3-dioxan-2-yl,benzimidazol-2-yl, dioxol-2-yl, oxadiazolyl, each of which is optionallymono- to trisubstituted in the ring moiety by halogen and/orstraight-chain or branched alkyl or alkoxy having 1 to 4 carbon atoms.

[0092] In a further very particularly preferred group of compounds, Ar¹represents mono- to tetrasubstituted phenyl, where the substituents areselected from the list below:

[0093] halogen, cyano, in each case straight-chain or branched alkyl orhalogenoalkyl having in particular 1 to 4 carbon atoms.

[0094] In general, X represents, in particular, fluroine or chlorine.

[0095] Particular preference is given to compounds in which X representsfluorine.

[0096] In general, L¹, L², L³, L⁴ and L⁵ are identical or different andindependently of one another each represents in particular hydrogen,halogen, cyano, nitro, formyl, alkylcarbonyl, alkoxycarbonyl,aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl having in eachcase 1 to 6 carbon atoms, alkyl, alkoxy, alkylthio, alkylsulphinyl oralkylsulphonyl having in each case 1 to 6 carbon atoms and being in eachcase optionally substituted by 1 to 5 halogen atoms, or

[0097] L¹, L², L³ and L⁴ are identical or different and independently ofone another each represents in particular hydrogen, halogen, cyano,nitro, formyl, alkylcarbonyl, alkoxycarbonyl, aminocarbonyl,alkylaminocarbonyl, dialkylaminocarbonyl having in each case 1 to 6carbon atoms, alkyl, alkoxy, alkylthio, alkylsulphinyl or alkylsulphonylhaving in each case 1 to 6 carbon atoms and being in each caseoptionally substituted by 1 to 5 halogen atoms and

[0098] L⁵ represents in particular one of the groups below:

[0099] where * denotes the point of attachment to the phenyl radical.

[0100] Preference is given to compounds in which L¹, L², L³ and L⁴ areidentical or different and independently of one another each preferablyrepresents hydrogen, fluorine, chlorine, bromine, cyano, nitro, acetyl,propionyl, methoxycarbonyl, ethoxycarbonyl, methylaminocarbonyl,ethylaminocarbonyl, dimethylaminocarbonyl, diethylaminocarbonyl, methyl,ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- ori-propoxy, methylthio, ethylthio, methylsulphinyl, ethylsulphinyl,methylsulphonyl or ethylsulphonyl, trifluoromethyl, trifluoroethyl,difluoromethoxy, trifluoromethoxy, difluorochloromethoxy,trifluoroethoxy, difluoromethylthio, difluorochloromethylthio,trifluoromethylthio, trifluoromethylsulphinyl ortrifluoromethylsulphonyl.

[0101] In a very particularly preferred group of compounds, L¹, L², L³and L⁴ each represent hydrogen or methyl.

[0102] In a further very particularly preferred group of compounds, L¹,L², L³ and L⁴ each represent hydrogen.

[0103] Preference is given to compounds in which L⁵ represents one ofthe groups below:

[0104] where * denotes the point of attachment to the phenyl radical.

[0105] In a very particularly preferred group of compounds, L⁵represents one of the groups below:

[0106] where * denotes the point of attachment to the phenyl radical.

[0107] The abovementioned general or preferred radical definitions applyboth to the end products of the formula (I) and, correspondingly, to thestarting materials or intermediates required in each case for thepreparation.

[0108] Independently of the combination of radicals given in each case,the definitions of radicals given in the combinations or preferredcombinations of radicals in question specifically for these radicals canalso be replaced by any definitions of radicals of other preferredranges.

[0109] It is extremely surprising that, in the process according to theinvention, aryloxyhalogenopyrimidine derivatives react with highselectivity and yield to give asymmetric 4,6-bis(aryloxy)pyrimidinederivatives when from 2 to 40 mol % of the tertiary amine1,4-diazabicyclo[2.2.2]octane (DABCO) are added. Since it is mentionedin the prior art (cf. EP-A1-794 177, U.S. Pat. No. 5,849,990 and U.S.Pat. No. 5,977,363) that this reaction requires at least a molarequivalent of a tertiary amine, it is extremely surprising that thisreaction can also be carried out with from 2 to 40 mol % of DABCO,giving excellent yields. This is confirmed by a comparative experimentin which the reaction was carried out without addition of DABCO (cf.Example 4, second step). The product can only be isolated in very pooryields.

[0110] The process according to the invention has a number ofadvantages. The asymmetric 4,6-bis(aryloxy)pyrimidine derivatives areobtained in high yields and purities. Moreover, it is possible to use,as starting materials, 4,6-difluoropyrimidine derivatives, which areeasier to obtain than 4,6-dichloropyrimidine derivatives. Traditionally,it is not necessary to recover the amine, since only catalytic amountsof DABCO are needed for carrying out the process.

[0111] The compounds of the formula (II) required as starting materialsfor carrying out the process according to the invention are known andcan be prepared by known methods (cf. DE-A1-197 10 609, WO 97/49605,DE-A1-196 42 533 and DE-A1-195 31299) or are commercially availableproducts.

[0112] The compounds of the formula (III) required as starting materialsfor carrying out the process according to the invention are customarycommercial products or can be prepared from the latter by simpleprocesses.

[0113] The compounds of the formula (V) required as starting materialsfor carrying out the process according to the invention are known andcan be prepared by known methods (cf. DE-A1 196 11 653, WO-A-95/24396,WO 95/04728, WO 97/27189, WO 97/14687, WO 98/23155, WO 98/21189, WO98/55461, WO 99/09026, WO 99/57116). All other starting materials arecustomary commercial products or can be prepared from the latter bysimple processes.

[0114] Suitable diluents for carrying out the first step of the processaccording to the invention are all inert organic solvents. Theseinclude, by way of example and by way of preference, aliphatic,alicyclic or aromatic hydrocarbons, such as, for example, petroleumether, hexane, heptane, cyclohexane, methylcyclohexane, benzene,toluene, xylene or decalin; halogenated hydrocarbons, such as, forexample, chlorobenzene, dichlorobenzene, dichloromethane, chloroform,carbon tetrachloride, dichloroethane or trichloroethane; ethers, suchas, for example, diethyl ether, diisopropyl ether, methyl-t-butyl ether,methyl-t-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane,1,2-diethoxyethane or anisole; ketones, such as, for example, acetone,butanone, methyl isobutyl ketone or cyclohexanone, nitriles, such as,for example, acetonitrile, propionitrile, n- or i-butyronitrile orbenzonitrile, amides, such as N,N-dimethylformamide,N,N-dimethylacetamide, N-methylformamide, N-methylpyrrolidone orhexamethylphosphoric triamide; esters, such as methyl acetate or ethylacetate; sulphoxides, such as dimethyl sulphoxide, sulphones, such assulpholane; or mixtures thereof with water. In the first step of theprocess according to the invention, preference is given to usingketones, in particular methyl isobutyl ketone.

[0115] The first step of the process according to the invention is, ifappropriate, carried out in the presence of a suitable acid acceptor.Suitable acid acceptors are all customary inorganic or organic bases.These include, by way of example and by way of preference, alkalineearth metal or alkali metal hydroxides, acetates, carbonates orbicarbonates, such as, for example, sodium hydroxide, potassiumhydroxide, sodium acetate, potassium acetate, sodium carbonate,potassium carbonate, potassium bicarbonate or sodium bicarbonate;tertiary amines, such as, for example, trimethylamine, triethylamine,tributylamine, N,N-dimethylaniline, N,N-dimethylbenzylamine, pyridine,N-methylpiperidine, N-methylmorpholine, N,N-dimethylaminopyridine,diazabicyclononene (DBN) oir diazabicycloundecene (DBU); and alsoalkaline earth metal or alkali metal hydrides, such as, for example,calcium hydride, sodium hydride or potassium hydride. In the first stepof the process according to the invention, preference is given to usingalkaline earth metal or alkalimetal carbonates, in particular potassiumcarbonate or sodium carbonate.

[0116] In the first step of the process according to the invention, thereaction temperatures can be varied within a relatively wide range. Ingeneral, the reaction is carried out at temperatures from 0° C. to 100°C., preferably at temperatures from 40° C. to 80° C.

[0117] For carrying out the process according to the invention, ingeneral from 1 to 4 mol, preferably from 1 to 1.1 mol, of the4,6-dichloropyrimidine derivatives of the formula (II) are employed permole of the compounds of the formula (III).

[0118] For carrying out the process according to the invention, ingeneral from 1 to 4 mol, preferably from 1 to 1.1 mol, of the4,6-dichloropyrimidine derivatives of the formula (II) are employed permole of the compounds of the formula (V).

[0119] For carrying out the first step of the process according to theinvention, the following procedure is generally adopted. The4,6-dichloropyrimidine derivative of the formula (II) is, if appropriatein the presence of a diluent, admixed with a base. The compound of theformula (III) or the compound of the formula (V) is added, ifappropriate in the presence of a diluent, and the mixture is, ifappropriate at elevated or at radius temperature, stirred until thereaction has gone to completion. After the reaction has ended, thereaction mixture is worked up in a customary manner or reacted directlyin situ in the second step of the process according to the invention.

[0120] The addition of compounds of the formula (III) or of compounds ofthe formula (V), if appropriate in the presence of diluent, in the firststep of the process according to the invention is carried out, inparticular, by metered addition to compounds of the formula (II)dissolved, if appropriate, in a ketone, in particular in methyl isobutylketone. The addition is carried out all at once or within a period of 12hours, preferably all at once or within a period of 6 hours.

[0121] Suitable diluents for carrying out the second step of the processaccording to the invention are all inert organic solvents. Theseinclude, by way of example and by way of preference, aliphatic,alicyclic or aromatic hydrocarbons, such as, for example, petroleumether, hexane, heptane, cyclohexane, methylcyclohexane, benzene,toluene, xylene or decalin; halogenated hydrocarbons, such as, forexample, chlorobenzene, dichlorobenzene, dichloromethane, chloroform,carbon tetrachloride, dichloroethane or trichloroethane; ethers, suchas, for example, diethyl ether, diisopropyl ether, methyl-t-butyl ether,methyl-t-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane,1,2-diethoxyethane or anisole; ketones, such as, for example, acetone,butanone, methyl isobutyl ketone or cyclohexanone, nitrites, such as,for example, acetonitrile, propionitrile, n- or i-butyronitrile orbenzonitrile, amides, such as N,N-dimethylformanilide,N,N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone orhexamethylphosphoric triamide; esters, such as methyl acetate or ethylacetate; sulphoxides, such as dimethyl sulphoxide, sulphones, such assulpholane; or mixtures thereof with water. In the second step of theprocess according to the invention, preference is given to usingketones, in particular methyl isobutyl ketone.

[0122] The second step of the process according to the invention is, ifappropriate, carried out in the presence of a suitable acid acceptor.Suitable acid acceptors are all customary inorganic or organic bases.These include, by way of example and by way of preference, alkalineearth metal or alkali metal hydroxides, acetates, carbonates orbicarbonates, such as sodium hydroxide, potassium hydroxide, sodiumacetate, potassium acetate, sodium carbonate, potassium carbonate,potassium bicarbonate or sodium bicarbonate; and also alkaline earthmetal or alkali metal hydrides, such as, for example, calcium hydride,sodium hydride or potassium hydride. In the second step of the processaccording to the invention, preference is given to using alkaline earthmetal or alkali metal carbonates, in particular potassium carbonate orsodium carbonate.

[0123] The second step of the process according to the invention iscarried out in the presence of catalytic amounts of1,4-diazabicyclo[2.2.2]octane (DABCO).

[0124] When carrying out the second step of the process according to theinvention, the reaction temperatures can be varied within a relativelywide range. In general, the reaction is carried out at temperatures offrom 0° C. to 100° C., preferably at temperatures of from 40° C. to 90°C., in particular at temperatures of from 50° C. to 80° C.

[0125] For carrying out the process according to the invention, ingeneral from 0.8 to 4 mol, preferably from 0.95 to 1.05 mol, of thecompounds of the formula (V) are employed per mole of the compounds ofthe formula (IV).

[0126] For carrying out the process according to the invention, ingeneral from 0.8 to 4 mol, preferably from 0.95 to 1.05 mol, of thecompounds of the formula (III) are employed per mole of the compounds ofthe formula (VI).

[0127] For carrying out the process according to the invention, ingeneral from 2 to 40 mol %, preferably from 2 to 20 mol %, of1,4-diazabicyclo[2.2.2]octane are employed per mole of the compounds offormula (IV).

[0128] For carrying out the process according to the invention, ingeneral from 2 to 40 mol %, preferably from 2 to 20 mol %, of1,4-diazabicyclo[2.2.2]octane are employed per mole of the compounds offormula (VI).

[0129] The second step of process variant a) is generally carried out asfollows. The compounds of the formula (V) are, if appropriate in thepresence of a diluent, admixed with a base and1,4-diazabicyclo[2.2.2]octane. The compounds of the formula (IV) areadded, if appropriate in the presence of the diluent, and the mixture isstirred, if appropriate at elevated temperature. After the reaction hasended, the reaction mixture is worked up in a customary manner.

[0130] Alternatively, the second step of process variant a) can also becarried out by admixing the compounds of the formula (IV), ifappropriate in the presence of a diluent, with a base and1,4-diazabicyclo[2.2.2]octane. The compounds of the formula (V) areadded, if appropriate in the presence of a diluent, and the mixture isstirred, if appropriate at elevated temperature. After the reaction hasended, the reaction mixture is worked up in a customary manner.

[0131] The second step of process variant b) is generally carried out asfollows. The compounds of the formula (III) are, if appropriate in thepresence of a diluent, admixed with a base and1,4-diazabicyclo[2.2.2]octane. The compounds of the formula (VI) areadded, if appropriate in the presence of the diluent, and the mixture isstirred, if appropriate at elevated temperature. After the reaction hasended, the reaction mixture is worked up in a customary manner.

[0132] Alternatively, process step b) can also be carried out byadmixing the compounds of the formula (VI), if appropriate in thepresence of a diluent, with a base and 1,4-diazabicyclo[2.2.2]octane.The compounds of the formula (III) are added, if appropriate in thepresence of a diluent, and the mixture is stirred, if appropriate atelevated temperature. After the reaction has ended, the reaction mixtureis worked up in a customary manner. In a specific variant, the processaccording to the invention is carried out as a one-pot reaction.

[0133] The examples below serve to illustrate the invention. However,the invention is not limited to the examples.

EXAMPLES Example 1

[0134] Process Variant a) or b)

4-Chloro-5-fluoro-6-[4-fluoro-3-(trifluoromethyl)phenoxy]pyrimidine

[0135]

[0136] (First Step)

[0137] 4,6-Dichloro-5-fluoropyrimidine (1.67 g, content: 98.9%) andpotassium carbonate (1.72 g) are initially charged in methyl isobutylketone (5 ml), and the mixture is, at 60° C., admixed dropwise over aperiod of 3 hours with a solution of 1.8 g of4-fluoro-3-(trifluoromethyl)phenol in 5 ml of methyl isobutyl ketone.The mixture is stirred at 60° C. for 1.5 hours and then cooled, admixedwith water, the organic phase is separated off, the aqueous phase isextracted once more with methyl isobutyl ketone, the organic extractsare combined and dried over sodium sulphate and the solvent is distilledoff. This gives4-chloro-5-fluoro-6-[4-fluoro-3-(trifluoromethyl)phenoxy]pyrimidine(2.74 g, content: 93.9%, 83.8% of theory) as an oil.

4-[4-Chloro-3-(trifluoromethyl)phenoxy]-5-fluoro-6-[4-fluoro-3-(trifluoromethyl)phenoxy]pyrimidine

[0138]

[0139] (Second Step)

[0140] 4-Chloro-3-(trifluoromethyl)phenol (0.98 g) together withpotassium carbonate (0.9 g) and 1,4-diazabicyclo[2.2.2]octane (DABCO)(28 mg), is initially charged in a methyl isobutyl ketone/water mixture(8 ml, 7/1), and, at 70-80° C., admixed with a solution of4-chloro-5-fluoro-6-[4-fluoro-3-(trifluoromethyl)phenoxy]pyrimidine(1.56 g, content: 98.8%) in 7 ml of methyl isobutyl ketone. The mixtureis stirred at 70-80° C. for 2 hours and then cooled, water is added, theorganic phase is separated off, the aqueous phase is extracted withmethyl isobutyl ketone, the combined organic extracts are dried oversodium sulphate and the solvent is distilled off. This gives4-[4-chloro-3-(trifluoromethyl)phenoxy]-5-fluoro-6-[4-fluoro-3-(trifluoromethyl)phenoxy]pyrimidine(1.92 g, content: 96.5%, 79.2% of theory) as a solid.

Example 2

[0141] Process Variant a)

4-Chloro-6-(3-chloro-2-methylphenoxy)-5-fluoropyrimidine

[0142]

[0143] (First Step)

[0144] 4,6-Dichloro-5-fluoropyrimidine (16,7 g, content: 99.7%) andpotassium carbonate (20.2 g) are initially charged in methyl isobutylketone (50 ml), and, at 60° C., admixed dropwise over a period of 3.5hours with a solution of 14.3 g of 3-chloro-2-methylphenol in 50 ml ofmethyl isobutyl ketone. The mixture is stirred at 60° C. for 2 hours andthen cooled, admixed with water, the organic phase is separated off, theaqueous phase is extracted once more with methyl isobutyl ketone, theorganic extracts are combined and dried over sodium sulphate and thesolvent is distilled off. This gives4-chloro-6-(3-chloro-2-methylphenoxy)-5-fluoropyrimidine (26.8 g,content: 96.7%, 95.2% of theory) as a solid.

(2E)-2-(2-{[6-(3-Chloro-2-methylphenoxy)-5-fluoro-4-pyrimidinyl]oxy}phenyl)-2-(methoxyimino)-N-methylethanamide

[0145]

[0146] (Second Step)

[0147] (2E)-2-(2-Hydroxyphenyl)-2-(methoxyimino)-N-methylethanamide(4.16 g, content: 99.7%), together with potassium carbonate (3.7 g) andDABCO (110 mg), is initially charged in methyl isobutyl ketone (30 ml),and, at 50° C., admixed with a solution of4-chloro-6-(3-chloro-2-methylphenoxy)-5-fluoropyrimidine (5.46 g,content: 98.1%) in 30 ml of methyl isobutyl ketone. The mixture isstirred at 50° C. for 4 hours and then cooled, water is added, theorganic phase is separated off, the aqueous phase is extracted withmethyl isobutyl ketone, the combined organic extracts are dried oversodium sulphate and the solvent is distilled off. This gives(2E)-2-(2-{[6-(3-chloro-2-methylphenoxy)-5-fluoro-4-pyrimidinyl]oxy}phenyl)-2-(methoxyimino)-N-methylethanamide(9.15 g, content: 94.2%, 96.9% of theory) as an oil.

Example 3

[0148] Process Variant a)

4-Chloro-6-(2-chlorophenoxy)-5-fluoropyrimidine

[0149]

[0150] (First Step)

[0151] 4,6-Dichloro-5-fluoropyrimidine (33.5 g, content: 98.9%) andpotassium carbonate (34.4 g) are initially charged in a methyl isobutylketone/water mixture (120 ml, 5/1) and, at 60° C., admixed dropwise overa period of 3 hours with a solution of 25.7 g of o-chlorophenol in 100ml of methyl isobutyl ketone. The mixture is stirred at 60° C. for 6hours and then cooled, the organic phase is separated off and washedwith 5% NaOH, the aqueous phase is extracted with methyl isobutylketone, the organic extracts are combined and dried over sodium sulphateand the solvent is distilled off. This gives4-chloro-6-(2-chlorophenoxy)-5-fluoropyrimidine (48.4 g, content: 95.6%,90.3% of theory) as an oil.

(E)-(2-{[6-(2-Chlorophenoxy)-5-fluoro-4-pyrimidinyl]oxy}phenyl)-(5,6-dihydro-1,4,2-dioxazin-3-yl)methanoneO-methyloxime

[0152]

[0153] (Second Step)

[0154] (E)-5,6-Dihydro-1,4,2-dioxazin-3-yl-(2-hydroxyphenyl)methanoneO-methyloxime (11.8 g), together with potassium carbonate (9.0 g) andDABCO (280 mg), is initially charged in a methyl isobutyl ketone/watermixture (80 ml, 7/1) and, at 80° C., admixed with a solution of4-chloro-6-(2-chlorophenoxy)-5-fluoropyrimidine (13.1 g, content: 98.1%)in 70 ml of methyl isobutyl ketone. The mixture is stirred at 80° C. for1.5 hours and then cooled, water is added, the organic phase isseparated off, the aqueous phase is extracted with methyl isobutylketone, the combined organic extracts are dried over sodium sulphate andthe solvent is distilled off. This gives(E)-2-(2-{[6-(2-chlorophenoxy)-5-fluoro-4-pyrimidinyl]oxy}phenyl)-(5,6-dihydro-1,4,2-dioxazin-3-yl)methanoneO-methyloxime (23.4 g, content: 95.2%, 97.9% of theory) as a solid.

Example 4

[0155] Process Variant a)

4-Chloro-6-(2-chlorophenoxy)-5-fluoropyrimidine

[0156]

[0157] (First Step)

[0158] 4,6-Dichloro-5-fluoropyrimidine (33.5 g, content: 98.9%) andpotassium carbonate (34.4 g) are initially charged in a methyl isobutylketone/water mixture (120 ml, 5/1), and, at 60° C., admixed dropwiseover a period of 3 hours with a solution of 25.7 g of o-chlorophenol in100 ml of methyl isobutyl ketone. The mixture is stirred at 60° C. for 6hours and then cooled, the organic phase is separated off and washedwith 5% NaOH, the aqueous phase is extracted with methyl isobutylketone, the organic extracts are combined and dried over sodium sulphateand the solvent is distilled off. This gives4-chloro-6-(2-chlorophenoxy)-5-fluoropyrimidine (48.4 g, content: 95.6%,90.3% of theory) as an oil.

(E)-(2-{[6-(2-Chlorophenoxy)-5-fluoro-4-pyrimidinyl]oxy}phenyl)-(5,6-dihydro-1,4,2-dioxazin-3-yl)methanoneO-methyloxime

[0159]

[0160] (Second Step, Comparative Experiment)

[0161] (E)-5,6-Dihydro-1,4,2-dioxazin-3-yl-(2-hydroxyphenyl)methanoneO-methyloxime (11.8 g) and potassium carbonate (9.0 g) are initiallycharged in a methyl isobutyl ketone/water mixture (80 ml, 7/1), and, at50° C., admixed with a solution of4-chloro-6-(2-chlorophenoxy)-5-fluoropyrimidine (13.1 g, content: 98.1%)in 70 ml of methyl isobutyl ketone. The mixture is stirred at 50° C. for24 hours and then cooled, water is added, the organic phase is separatedoff, the aqueous phase is extracted with methyl isobutyl ketone, thecombined organic extracts are dried over sodium sulphate and the solventis distilled off. This gives(E)-2-(2-{[6-(2-chlorophenoxy)-5-fluoro-4-pyrimidinyl]oxy}phenyl)-(5,6-dihydro-1,4,2-dioxazin-3-yl)methanoneO-methyloxime (26.4 g, content: 33.3%, 38.6% of theory) as an oil.

Example 5

[0162] Process Variant b)

(E)-{2-[(6-Chloro-5-fluoro-4-pyrimidinyl)oxy]phenyl}(5,6-dihydro-1,4,2,-dioxazin-3-yl)methanoneO-methyloxime

[0163]

[0164] (First Step)

[0165] 4,6-Dichloro-5-fluoropyrimidine (31.8 g, content: 98.9%) andpotassium carbonate (31.5 g) are initially charged in acetone (115 ml),and, at 60° C., admixed dropwise over a period of 6 hours with asolution of 44.9 g of(E)-5,6-dihydro-1,4,2-dioxazin-3-yl-(2-hydroxyphenyl)methanoneO-methyloxime in 350 ml of acetone. The mixture is stirred at 60° C. for2 hours, the acetone is distilled off, the mixture is admixed withmethylene chloride and water, the organic phase is separated off, theaqueous phase is extracted with methylene chloride, the organic extractsare combined, washed with 5% NaOH and dried over sodium sulphate and thesolvent is distilled off. This gives(E)-{2-[(6-chloro-5-fluoro-4-pyrimidinyl)oxy]phenyl}-(5,6-dihydro-1,4,2,-dioxazin-3-yl)methanoneO-methyloxime (68.0 g, content: 95.8%, 94.5% of theory) as a solid.

Patent claims
 1. Process for preparing compounds of the general formula(I),

in which Ar¹ represents in each case substituted or unsubstituted arylor heterocyclyl, X represents hydrogen, fluorine, chlorine or bromine,L¹, L², L³, L⁴ and L⁵ are identical or different and independently ofone another each represents hydrogen, halogen, cyano, nitro,alkylcarbonyl formyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl,dialkylaminocarbonyl, in each case optionally halogen-substituted alkyl,alkoxy, alkylthio, alkylsulphinyl or alkylsulphonyl, or L¹, L², L³ andL⁴ are identical or different and independently of one another eachrepresents hydrogen, halogen, cyano, nitro, alkylcarbonyl, formyl,alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl,in each case optionally halogen-substituted alkyl, alkoxy, alkylthio,alkylsulphinyl or alkylsulphonyl, and L⁵ represents one of the groupsbelow:

where * denotes the point of attachment to the phenyl radical, and wherethe radicals Ar¹ and

are different, characterized in that 4,6-dichloropyrimidine derivativesof the general formula (II),

in which X is as defined above, a) are initially, in a first step,reacted with compounds of the general formula (III), Ar¹—OH,  (III)  inwhich Ar¹ is as defined above, if appropriate in the presence of adiluent and if appropriate in the presence of an acid acceptor, and theresulting compounds of formula (IV),

 in which Ar¹ and X are each as defined above are then, in a secondstep, reacted with compounds of the general formula (V),

 in which L¹, L², L³, L⁴ and L⁵ are each as defined above, ifappropriate in the presence of a solvent, if appropriate in the presenceof a base and with addition of from 2 to 40 mol % of1,4-diazabicyclo[2.2.2]octane (DABCO), or b) are initially, in a firststep, reacted with compounds of the general formula (V),

 in which L¹, L², L³, L⁴ and L⁵ are each as defined above, ifappropriate in the presence of a diluent and if appropriate in thepresence of an acid acceptor, and the resulting compounds of the formula(VI),

 in which X, L¹, L², L³, L⁴ and L⁵ are each as defined above, are then,in a second step, reacted with compounds of general formula (III),Ar¹—OH,  (III)  in which Ar¹ is as defined above, if appropriate in thepresence of a solvent, if appropriate in the presence of a base and withaddition of from 2 to 40 mol % of 1,4-diazabicyclo[2.2.2]octane (DABCO).2. Process according to claim 1, characterized in that, for carrying outthe process according to the invention for preparing the compounds ofthe formula (I), from 2 to 20 mol % of 1,4-diazabicyclo[2.2.2]octane areused per mole of the compound of the formula (IV).
 3. Process accordingto claim 1, characterized in that, for carrying out the processaccording to the invention for preparing the compounds of the formula(I), from 2 to 20 mol % of 1,4-diazabicyclo[2.2.2]octane are used permole of the compound of the formula (VI).
 4. Process according to atleast one of claims 1 to 3, characterized in that the process forpreparing the compounds of the formula (I) is carried out as a one-potprocess.
 5. Process according to at least one of claims 1 to 4,characterized in that from 1 to 4 mol of the 4,6-dichloropyrimidinederivative of the formula (II) are employed per mole of the compounds ofthe formula (III).
 6. Process according to at least one of claims 1 to4, characterized in that from 1 to 4 mol of the 4,6-dichloropyrimidinederivative of the formula (II) are employed per mole of the compounds ofthe formula (V).
 7. Process according to at least one of claims 1 to 6,characterized in that from 0.8 to 4 mol of the compounds of formula (V)are employed per mole of the compounds of the formula (IV).
 8. Processaccording to at least one of claims 1 to 6, characterized in that from0.8 to 4 mol of the compounds of formula (III) are employed per mole ofthe compounds of the formula (VI).
 9. Process according to at least oneof claims 1 to 8, characterized in that Ar¹ represents heterocyclylhaving 3 to 7 ring members which is optionally substituted by halogen orby alkyl, alkoxy, halogenoalkyl, halogenoalkoxy having in each case 1 to4 carbon atoms; or represents phenyl or naphthyl, each of which isoptionally mono- to tetrasubstituted by identical or differentsubstituents, the possible substituents preferably being selected fromthe list below: halogen, cyano, nitro, formyl, carboxyl, carbamoyl,thiocarbamoyl; in each case straight-chain or branched alkyl, oxoalkyl,alkoxy, alkoxyalkyl, alkylthioalkyl, dialkoxyalkyl, alkylthio,alkylsulphinyl or alkylsulphonyl having in each case 1 to 8 carbonatoms; in each case straight-chain or branched alkenyl or alkenyloxyhaving in each case 2 to 6 carbon atoms; in each case straight-chain orbranched halogenoalkyl, halogenoalkoxy, halogenoalkylthio,halogenoalkylsulphinyl or halogenoalkylsulphonyl having in each case 1to 6 carbon atoms and 1 to 13 identical or different halogen atoms; ineach case straight-chain or branched halogenoalkenyl orhalogenoalkenyloxy having in each case 2 to 6 carbon atoms and 1 to 11identical or different halogen atoms; in each case straight-chain orbranched dialkylamino; alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl,alkylaminocarbonyl, dialkylaminocarbonyl, arylalkylaminocarbonyl,dialkylaminocarbonyloxy, alkenylcarbonyl or alkinylcarbonyl, having 1 to6 carbon atoms in the respective hydrocarbon chain; cycloalkyl orcycloalkyloxy having in each case from 3 to 6 carbon atoms; in each casedoubly attached alkylene having 3 or 4 carbon atoms, oxyalkylene having2 or 3 carbon atoms or dioxyalkylene having 1 or 2 carbon atoms, each ofwhich is optionally mono- to tetrasubstituted by identical or differentsubstituents from the group consisting of fluorine, chlorine, oxo,methyl, trifluoromethyl and ethyl;  or a grouping

in which A¹ represents hydrogen, hydroxyl or alkyl having 1 to 4 carbonatoms or cycloalkyl having 1 to 6 carbon atoms and A² representshydroxyl, methoxy, ethoxy, amino, methylamino, phenyl, benzyl orrepresents in each case optionally cyano-, alkoxy-, alkylthio-,alkylamino-, dialkylamino- or phenyl-substituted alkyl or alkoxy having1 to 4 carbon atoms, or represents alkenyloxy or alkinyloxy having ineach case 2 to 4 carbon atoms, and also phenyl, benzoyl, benzoylethenyl,cinnamoyl, heterocyclyl or phenylalkyl, phenylalkyloxy orheterocyclylalkyl, having in each case 1 to 3 carbon atoms in therespective alkyl moieties and being in each case optionally mono- totrisubstituted in the ring moiety by halogen and/or straight-chain orbranched alkyl or alkoxy having 1 to 4 carbon atoms, X representsfluorine or chlorine, L¹, L², L³, L⁴ and L⁵ are identical or differentand independently of one another each represents hydrogen, halogen,cyano, nitro, formyl, alkylcarbonyl, alkoxycarbonyl, aminocarbonyl,alkylaminocarbonyl, dialkylaminocarbonyl having in each case 1 to 6carbon atoms, alkyl, alkoxy, alkylthio, alkylsulphinyl or alkylsulphonylhaving in each case 1 to 6 carbon atoms and being in each caseoptionally substituted by 1 to 5 halogen atoms, or L¹, L², L³ and L⁴ areidentical or different and independently of one another each representshydrogen, halogen, cyano, nitro, formyl, alkylcarbonyl, alkoxycarbonyl,aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl having in eachcase 1 to 6 carbon atoms, alkyl, alkoxy, alkylthio, alkylsulphinyl oralkylsulphonyl having in each case 1 to 6 carbon atoms and being in eachcase optionally substituted by 1 to 5 halogen atoms and L⁵ representsone of the groups below:

where * denotes the point of attachment to the phenyl radical. 10.Process according to at least one of claims 1 to 8, characterized inthat Ar¹ represents optionally methyl-, ethyl-, methoxy-, ethoxy-,trifluoromethyl- or trifluoromethoxy-substituted thienyl, pyridyl orfuryl; or represents phenyl which is in each case optionally mono- totetrasubstituted by identical or different substituents, the possiblesubstituents preferably being selected from the list below: fluorine,chlorine, bromine, iodine, cyano, nitro, formyl, carboxyl, carbamoyl,thiocarbamoyl, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, 1-,2-, 3-, neo-pentyl, 1-, 2-, 3-, 4-(2-methylbutyl), 1-, 2-, 3-hexyl, 1-,2-, 3-, 4-, 5-(2-methylpentyl), 1-, 2-, 3-(3-methylpentyl),2-ethylbutyl, 1-, 3-, 4-(2,2-dimetylbutyl), 1-, 2-(2,3-dimethylbutyl),3-oxobutyl, methoxymethyl, dimethoxymethyl, methoxy, ethoxy, n- ori-propoxy, methylthio, ethylthio, n- oder i-propylthio, methylsulphinyl,ethylsulphinyl, methylsulphonyl or ethylsulphonyl, vinyl, allyl,2-methylallyl, propene-1-yl, crotonyl, propargyl, vinyloxy, allyloxy,2-methylallyloxy, propene-1-yloxy, crotonyloxy, propargyloxy,trifluoromethyl, trifluoroethyl, difluoromethoxy, trifluoromethoxy,difluorochloromethoxy, trifluoroethoxy, difluoromethylthio,trifluoromethylthio, difluorochloromethylthio, trifluoromethylsulphinylor trifluoromethylsulphonyl, dimethylamino, diethylamino, acetyl,propionyl, methoxycarbonyl, ethoxycarbonyl, methylaminocarbonyl,ethylaminocarbonyl, dimethylaminocarbonyl, diethylaminocarbonyl,dimethylaminocarbonyloxy, diethylaminocarbonyloxy, benzylaminocarbonyl,acryloyl, propioloyl, cyclopentyl, cyclohexyl, in each case doublyattached propanediyl, ethyleneoxy, each of which is optionally mono- totetrasubstituted by identical or different substituents from the groupconsisting of fluorine, chlorine, oxo, methyl and trifluoromethyl,  or agrouping

where A¹ represents hydrogen, methyl or hydroxyl and A² representshydroxyl, methoxy, ethoxy, amino, methylamino, phenyl or benzyl, andalso phenyl, benzoyl, benzoylethenyl, cinnamoyl, benzyl, phenylethyl,phenylpropyl, benzyloxy, 5,6-dihydro-1,4,2-dioxazin-3-ylmethyl,triazolylmethyl, benzoxazol-2-ylmethyl, 1,3-dioxan-2-yl,benzimidazol-2-yl, dioxol-2-yl, oxadiazolyl, each of which is optionallymono- to trisubstituted in the ring moiety by halogen and/orstraight-chain or branched alkyl or alkoxy having 1 to 4 carbon atoms, Xrepresents fluorine, L¹, L², L³ and L⁴ are identical or different andindependently of one another each represents hydrogen, fluorine,chlorine, bromine, cyano, nitro, acetyl, propionyl, methoxycarbonyl,ethoxycarbonyl, methylaminocarbonyl, ethylaminocarbonyl,dimethylaminocarbonyl, diethylaminocarbonyl, methyl, ethyl, n- ori-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy,methylthio, ethylthio, methylsulphinyl, ethylsulphinyl, methylsulphonylor ethylsulphonyl, trifluoromethyl, trifluoroethyl, difluoromethoxy,trifluoromethoxy, difluorochloromethoxy, trifluoroethoxy,difluoromethylthio, difluorochloromethylthio, trifluoromethylthio,trifluoromethylsulphinyl or trifluoromethylsulphonyl, and L⁵ representsone of the groups below:

where * denotes the point of attachment to the phenyl radical. 11.Process according to at least one of claims 1 to 8, characterized inthat Ar¹ represents optionally methyl-, ethyl-, methoxy-, ethoxy-,trifluoromethyl- or trifluoromethoxy-substituted thienyl, pyridyl orfuryl; or represents phenyl which is in each case optionally mono- totetrasubstituted by identical or different substituents, the possiblesubstituents preferably being selected from the list below: fluorine,chlorine, bromine, iodine, cyano, nitro, formyl, carboxyl, carbamoyl,thiocarbamoyl, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, 1-,2-, 3-, neo-pentyl, 1-, 2-, 3-, 4-(2-methylbutyl), 1-, 2-, 3-hexyl, 1-,2-, 3-, 4-, 5-(2-methylpentyl), 1-, 2-, 3-(3-methylpentyl),2-ethylbutyl, 1-, 3-, 4-(2,2-dimetylbutyl), 1-, 2-(2,3-dimethylbutyl),3-oxobutyl, methoxymethyl, dimethoxymethyl, methoxy, ethoxy, n- ori-propoxy, methylthio, ethylthio, n- oder i-propylthio, methylsulphinyl,ethylsulphinyl, methylsulphonyl or ethylsulphonyl, vinyl, allyl,2-methylallyl, propene-1-yl, crotonyl, propargyl, vinyloxy, allyloxy,2-methylallyloxy, propene-1-yloxy, crotonyloxy, propargyloxy,trifluoromethyl, trifluoroethyl, difluoromethoxy, trifluoromethoxy,difluorochloromethoxy, trifluoroethoxy, difluoromethylthio,trifluoromethylthio, difluorochloromethylthio, trifluoromethylsulphinylor trifluoromethylsulphonyl, dimethylamino, diethylamino, acetyl,propionyl, methoxycarbonyl, ethoxycarbonyl, methylaminocarbonyl,ethylaminocarbonyl, dimethylaminocarbonyl, diethylaminocarbonyl,dimethylaminocarbonyloxy, diethylaminocarbonyloxy, benzylaminocarbonyl,acryloyl, propioloyl, cyclopentyl, cyclohexyl, in each case doublyattached propanediyl, ethyleneoxy, each of which is optionally mono- totetrasubstituted by identical or different substituents from the groupconsisting of fluorine, chlorine, oxo, methyl and trifluoromethyl,  or agrouping

where A¹ represents hydrogen, methyl or hydroxyl and A² representshydroxyl, methoxy, ethoxy, amino, methylamino, phenyl or benzyl, andalso phenyl, phenoxy, phenylthio, benzoyl, benzoylethenyl, cinnamoyl,benzyl, phenylethyl, phenylpropyl, benzyloxy, benzylthio,5,6-dihydro-1,4,2-dioxazin-3-ylmethyl, triazolylmethyl,benzoxazol-2-ylmethyl, 1,3-dioxan-2-yl, benzimidazol-2-yl, dioxol-2-yl,oxadiazolyl, each of which is optionally mono- to trisubstituted in thering moiety by halogen and/or straight-chain or branched alkyl or alkoxyhaving 1 to 4 carbon atoms, X represents fluorine, L¹, L², L³ and L⁴each represent hydrogen, and L⁵ represents one of the groups below:

where * denotes the point of attachment to the phenyl radical.